Process for dyeing fibre mixtures of polyester and wool

ABSTRACT

MIXTURE OF POLYESTER FIBRES AND WOOL ARE DYES SIMULTANEOUSLY WITH DISPERSE DYESTUFFS AND WOOL DYESTUFFS IN THE PRESENCE OF SODIUM O-PHENYLPHENOLATE, A LEVELLING AGENT, AND A WOOL RESERVE AGENT. THE SODIUM O-PHENYLPHENOLATE PROMOTES THE PENETRATION OF THE DISPERSE DYESTUFF INTO THE POLYESTER FIBRES AND THE OTHER ADDITIVES PREVENT DEMIXING OF THE O-PHENYLPHENOLATE CARRIER.

ABSTRACT on THE DISCLOSURE Mixture of polyester fibres and wool are dyed simultaneously with disperse dyestuffs and wool dyestuffs in the presence of sodium o-phenylphenola te, a levelling agent, and a wool reserve agent. The sodium o-phenylphenolate promotes the penetration of the disperse dyestuff into the polyester fibres and the other additives prevent demixing of the o-phenylphenolate carrier.

This is a continuation of application Ser. No. 849,859, filed Aug. 13, 1969, now abandoned.

The presentinventiont. relates to a process for dyeing fibre mixtures of polyesters and wool, with the polyester portion being dyed with dispersion dyestuffs and the wool being dyed with wool dyestuffs and in the presence of ophenylphenol as a carrier'in baths towhich an aqueous stable carrier preparation is added in addition to the dyestuffs. The process is characterized in that the carrier preparation contains (a) the sodium salt of o-phenylphenol, (b) a levelling agent and (c) a wool reserve agent ,which has affinity for the fibre, with the quantity ratio (a) :(b) (c) lying in the range of (20 to 60) (5 to 20) (2 to 20) and with the dyebath containing 2 to 15%, relative to the material to be dyed, of the sodium salt of o'- phenylphenol. 1 i

Particularly suitable aqueous. carrier preparations are those containing (a) the sodium salt or potassium salt of .o-phenylphenol, (b) at least one addition compound of 5 to 70 mols of ethylene oxide to monoamines or diamines, with at least one nitrogen a'tom of theamine being substituted by a hydrocar'bon'residue having 16 to 22 carbon 'atoms, as a levelling agent, and (c), at least one condensation product of formaldehyde and (a) sulphones which possess two phenol residues bonded to the SO: groups or (b') hydroxybenzenesulphonic or naphthalenesulphonic acidsas a wool reserve agent having aflinity for the fibre,

with the quantity ratio (a):(b):(c) lying in the range (20 to 60);(5 .to,20).:(2 to 20) and with the dyebath containing 2 to 15%, relative to the material to be dyed, of the sodium or potassium salt of o-phenylphenol.

. It is known to use ortho phenylphenol and para-phenylphenol as carriers for dyeing polyester material or material containing polyesters. These carriers are intended to pro- "mote' the penetration of the dyestulf and better complete dyeing of the polyester fibre,-since, as the polyesters lack functional groups and their ability to swell in water is only slight, dyeing withnormal dyebaths in most cases does not produce usable results.

When using prefabricated carrier preparations as auxiliary agents for dyeing polyestertmaterial care must be taken that the carrier dispersion does not demix or that a constituent crystallizes out.- These disadvantages occur in the case of all known carrier preparations which contain ortho-phenylphenol and thus these preparations can only be added to the goods to be dyed when the preparations are in the form of an emulsion or solution, for which special measures, for example boiling the preparation, are

- United States Patent 3,809,532 Patented May 7, 1974 in most cases necessary. On cooling such emulsions the ortho-phenylphenol again crystallizes out.

It has now been found that an aqueous carrier preparation which in addition to o-phenylphenol as the actual to 60:40 and in the most diverse processingconditions', for

example in a loose form, as combed tops, yarn or amixed woven fabric.

In this process wool is dyed with wool dyestuffs which can be reactive or non-reactive towards the substrate to be dyed and which can belongto the most diverse classes of dyestuffs, especially classes of the acid azo and anthraquinone dyestuffs, but also of the ,azomethine dyestuffs; The chromium and cobalt complexes of monoazo dyestuffs which contain more than one molecule of dyestufl per atom of metal bound as a complex, with at least one dyestuff molecule being free of sulphonic acid groups and of carboxylic acid groups not participating in the complex formation, prove to be particularly advantageous. The heavy metal atom can be bonded to two mutually different or two identical dyestuff molecules. The complex-forming group of the dyestuffs can for example be a o-hydroxy-o-aminoazo grouping, a o-hydroxy-o'-carboxyazo grouping or preferably an o,o'-dihydroxyazo grouping.

By reactive dyestuffs there are to be understood those dyestuffs which can enter a chemical, that is to say covalent, bond with the material to be dyed. These dyestuffs for example contain ethyleneimide, epoxy, vinyl, vinylsulphonic or acrylic acid groups or halogenated groups such as u,fl-dibromopropionic acid, fl-chloropropionic acid, a or fi-brornacrylic acid residues or monohalogenated or dihalogenated triazinyl and pyrimidyl residues, as reactive residue of a long-chain fatty acid; furthermore these adducts can also be quaternized at a nitrogen atom or be esterified with a polybasic acid at the end of a polyglycol chain, or be both quaternized and esterified.

As starting substances, single higher-molecular 'alkylamines or also amine mixtures, such as are obtained on conversion of natural fatty acid mixtures, for example tallow fatty acid, into the corresponding amines are used. Amines with 16 to 22 carbon atoms to which 5 to at most 70 mols of ethylene oxide have been added on are suitable. The following may be mentioned individually as amines: hexadecylamine, octodecylamine, arachidylamine behenylamine CH (CH -NH octodecenylamine and N-alkylpropylenediamines with the appropriate hydrocarbon residues;

The wool reserve agents are colorless compounds having aflinity for the'fibre'are for example water-soluble condensation products of formaldehyde and mixtures of 'have further substituents, bonded to the SO group, and (b) monocyclic hydroxyarylsulphonic acids 'or' bicyclic arylsulphonic acids. Advantageously, mixtures are used in which the molecular quantity ratio of (a) sulphone to (b) sulphonic acid is 30:70 to 85: 15.

However, the individual components of the mixtures -of sulphones and sulphonic acids, such as for example I water-soluble condensation products of formaldehyde and sulphones which possess two phenol residues, which may have further substituents, bonded to the SO group, or :.hydroxybenzene-sulphonic acids or naphthalenesulphonic acids, are however also suitable;

Both the sulphones and thesulphonic acids and also .-their. reaction products with formaldehyde are compounds which are in themselvesknown. V Amongst the sulphones, the dihydroxydiphenylsulphones of formula R R are-preferred, wherein'R and R independently of one another denotehydrogen atoms, methyl groups'or sul phonic acid groups. Phenolsulphonic acids and cresolsul-' phonic acids may be mentioned as examples of the mono- 'cyclic hydroxyarylsulphonic acids.

The condensation of the mixtures with formaldehyde is appropriately carried out in an'aqueous alkaline me- 'dium. For example, a mixture of a sulphone and a $111- phonic acid of the nature indicated in water can be vrendered alkaline with sodium or potassium hydroxide, formaldehyde added (for example 0.9 to" 1.1 mols per mol of mixture of hydroxyaryl compounds) and the whole kept at an elevated temperature for a prolonged .period, for example 5 to 6 hours. Mixtures of sulphones and sulphonic acids can also be manufactured by reacting a hydroxybenzene such as phenol, p-cresol or a xylenol,

with concentrated sulphuric acid. Thereafter, when the.

.requisite quantity of alkali hydroxide has been added to establish the alkaline medium following the addition of water, the condensation with formaldehyde can be carriedout without an intermediate separation. A condensation under acid conditions, for example in acetic acid solution, is also possible.

In addition .to the mixtures of sulphone and sulphonic acidiwhich have been mentioned, the condensation products of formaldehyde with the diarylsulphones of the above-mentioned nature which possess at least one pheno- Hlic. hydroxyl group are also suitable to be used by themselves asa reserve agent. i

The limits of the components mentioned for the raqueous carrier preparation lie between 20 to 60 parts of orthophenylphenol, 5 to 20 parts of a levelling: agent and 2 to .20 parts of. a wool reserve agent having afiinity .ifor -the fibre, with the difference from 100 parts optionally being madeup with water. A clear solution of low viscosity which gives an alkaline reaction is obtained:

The amount of carrier preparation which is added-to the dyebath is 10 to 40% relative to the weight of the ,material to be dyed. The dyebath should react acid .dur- Iingthe dyeing process, and the pH-value should be about 5; therequisite acid reaction is achieved by adding low l molecular organic acids, especially formic acid-and acetic. acid, Following the dyeing process, the goods are appropriately. further treated for a short time with a dyebath rendered alkaline with ammonia and adjusted to pH 8, and are then rinsed and dried.

The advantages of the present process reside in the stability, which is good at room temperature also, and hence in the easy manipulation of the carrier preparation which is directly added.to the dyebath without prior dissolution. Furthermore the preparation improves the dispersion stability of the dispersion dyestuffs so that no vseparate addition of a dispersing agent to the dyebath'is necessary. The action of the reserv'e'agenthaving afiinity for the fibre resides in the fact that on each kind of fibre it is the dyestuff intended for the particular fibre which The levelling agent in the carrier preparation serves as an emulsifier for the actual carrier, the o-phenylphenol,

. but then also acts as a dispersing agent in the dyebath for the dispersion dyestuffs and naturally as a levelling agent for the wool dyestuffs.

The present process for dyeing fibre mixtures of wool and polyester fibres now has the advantagethat in addition to the dyestuif a stable aqueous carrier preparation is added to the dyebath, the auxiliary agent combination of the carrier preparation being on the one hand a dis- .persing agent and emulsifier for the actual .carrierbut on the other hand also a levelling agent for the dyestuffs 4 of the dyebath, with one ofthe components additionally MANUFACTURING INSTRUCTION FOR THE CARRIER PREPARATION v Parts Sodium salt of o-phenylphenol 50 'One of the levelling agents described below 10 7 -1 mol of a fatty amine (having a hydrocarbon residue of 18 to 22 carbon atoms) and 30 mols of ethylene oxv are stirred together at 50 to 60 Thereafter the mixture is slowly cooled to room temperature. 7

(1) Levelling agents C1 cnicmmnsomm R;N mNoonio wmornmm wherein R denotes the hydrocarbon residue of the tallow fatty amine and m-I- n) has an average value of 7, I

(b) 50% strength aqueous solution of a mixture of (1) an' adduct of 1 mol of tallow fatty amine anmzo mols of ethylene oxide, quaternized with dim e'thylsulpha'te and (2) the ammonium salt of the acid sulphuricjacid ester of the adduct of 1 mol of a fatty' amine (consisting of 10% 'stearylamine, 55% arachidylamine and 35% behenylamine) and 30 mols of ethylene oxide.

(c) 30% strength aqueous solutionfof an adduct'of 1 mol of a fatty amine (having a hydrocarbon residue of 18 to 22 carbon atoms) and 30 mols of ethylene oxide. ((1) 50% strength aqueous soltition of an adduct of 'ide, quaternized with dimethyl sulphate.

(e) 50% strength aqueous solution of an adduct'of 1 mol of a fatty amine (having a hydrocarbon residue of 16 to 20 carbon atoms) and mols of ethyleneoxide.

oil and 40 mols of ethylene oxide.

(f) 50% strength aqueous solution of the ammonium salt of the acid sulphuric acid ester of the adduct of 1 mol of tallow fatty amine and 30 mols of ethylene oxide.

(g) 50% strength aqueous solution of the ammonium (2) Reserve agent (a) 35 strength aqueous solution of a condensation product of formaldehyde and a mixture of 4,4-dihydroxydiphenylsulphone 3 sulphonic acid and o-cresol-4-sulphonic acid, which has been adjusted to a pH-value of 7 with 30% strength sodium hydroxide solution (molar ratio of sulphone to sulphonic acid, 40: 60).

(b) 35% strength aqueous solution of the condensation product (a), with a molar ratio of sulphone to sulphonic acid of 80:20.

(0) 35% strength aqueous solution of a condensation product of formaldehyde and 4,4 dihydroxydiphenylsulphone 3 sulphonic acid, which has been adjusted to a pH-value of 7 with 30% strength sodium hydroxide solution.

(d) 35% strength aqueous solution of a condensation product of formaldehyde and a mixture of 4,4 dihydroxy 3 methyldiphenylsulphone and l-hydroxy-Z- methylbenzene 4 sulphonic acid (molar ratio of sulphone to sulphonic acid, 40:60). Similar condensation products are obtained if 4,2'-dihydroxy-diphenylsulphone, 4,4 dihydroxy 3,3 dimethyl-diphenylsulphone or mixtures of these sulphones with l-hydroxy 2 methylbenzene 4 sulphonic acid or phenol 4 sulphonic acid are reacted with formaldehyde in the indicated manner.

(e) 50% strength aqueous solution of a condensation product of formaldehyde and a mixture of naphthalenesulphonic acid and 4,4'-dihydroxydiphenylsulphone.

(f) Condensation product of naphthalenesulphonic acid and formaldehyde. ll

(g) 50% strength aqueous solution of a condensation 6 EXAMPLE 1 A woven fabric consisting of 55% polyester and wool is washed, treated in the kier and pre-set for 30 secondsat180C.

100 kg. of this woven fabric are introduced into 4000 litres of water at 60 C. The following additives are then introduced into the bath: 8000 g. of ammonium sulphate,

4000 g. of 85% strength formic acid, 20,000 g. of the carrier preparation as, described'in the manufacturing instruction, using the, levellingagent (1)(a) and the reserve agent (2)-(a); 1000 g. of the dyestuii of formula mu t on and 800 g. of the dyestuif of formula 2 o NH A sour Y 11,0 cm-NH-oocrcn, d m l e The pH-value should be about 5.

The dyeing temperature is raised to 92-9-6 C. within 40 minutes and dyeing is carried out for 90 minutes at this temperature. The bath is then cooled to 80 C. and adjusted to a pH-value of 8 with ammonia, and the goods are treated for 20 minutes at 80 C., then rinsed warm and cold, and if desired acid-treated with 1% of 85% strengthformic acid.

A fast blue dyeing with good matching of the shades of the two kinds of fibre results. Instead of the indicated components for the preparation of the carrier, it is also possible to use the remaining products indicated in the manufacturing instruction, such as for example (1)(b) and (2)-(d) or (1)-(d) and (2)--(f).

product of formaldehyde and 4,4 dihydroxydiphenylsulphone 3 sulphonic acid which has been adjusted to a pH-value of 7 with strength sodium hydroxide solution. r

(h) 35% strength aqueous solution of a condensation product of phenolsulphonic acid and formaldehyde, which product of formaldehyde and a mixture of phenolsulphonic acid, 4,4 dihydroxydiphenylsulphone and 2- naphthol 6 sulphonic acid, which has been adjusted to a pH-value of 7.5 with 30% strength aqueous'sodium hydroxide solution (molar ratio phenolsulphonic acid to 4,4f-dihydroxydiphenylsulphone to 2-naphthol 6 sulphonic acid, 50:50:10).

In addition to the above-mentioned parts of the individual components for the preparation of the carrier, all variations within the limits mentionedare of course also possible which comprise 20 to 60 parts of the sodium salt of o-phenylphonol, 5 to 20 parts of the levelling agent and 2 to 20 parts of the wool reserve agent having affinity for the fibre.

.EXAMPLEZ 100 kg. of woven fabric consisting of 55% polyester and 45% .wool are pre-wetted in 4000 litres of water at 60 C. on aj winch. 8000 g. of ammonium sulphate and 3000 g. of strength formic acid are then added. After distributing these additives, 25,000 g. of the carrier preparation as described in the manufacturing instruction, using the-levelling agent (l)-(a) and the reserve agent (2)-(b), 1200 g. of the dyestutf .of formula (3) H2111 (HI 11m, and 800 g. of thedyestuff of formula t are ifurtheiadded to the bath. The pH-value of the bath is adjusted to 4.5-5.5.

.uctsindicatedin the manufacturing instruction. w

100 kg. oflcheeses consisting of 55 polyesterand 45% 'wool' are wetted in'2000'litres of .water at 60 C. in a 7 The bath is then warmed to the boil within 40 minutes and dyeing is carried out for 90-minutes at this temper- ;ature. Thereafter the bath iscooled to 80 C. and ad- ,justed to.a pI-l-value of 8;with ammonia, and the goods are further treated for 20 minutes, rinsed and dried. A

fast level blue dyeing of both kinds of fibre results. In-

stead of the indicatedcomponents for the preparation of ..the, carrier, i-t is also possible touse the remaining prod- EXAMPLE cheese dyeing apparatus. The following are then added: 4000 g. of ammonium sulphate, 3000 g. of 85% strength formic acid, 20,000 g. of the carrier preparation as described in the manufacturing instruction, using the levelling agent (1)-(c) and the reserve agent (2)-(b), 500

g. of the dyestutt of formula 250 g. of the dyestuff of formula 180 g. of the dyestuff of formula and 100 g. of the dyestulf of formula.

,(s) g V l H 01: 1.

H0. 000E I N N=NI-C\/I l I The pH-value of'the dyeb a'th'is adjusted to"4'.55.5. The 55 temperature is raised to 106 C. within minutes and dyeing carried out for minutes at this temperature. Thereafter the dyebath is cooled and the goods are rinsed and dried.

A level fast yellow dyeing of both fibre portions results. 60

Instead of the indicated components for the preparation of the carrier, it is also possible to use the remaining products indicated in the manufacturing instruction.

100 kg. of yarn consisting of polyester fibres and 45% wool, are dyed in a cheese dyeing apparatus in the following manner I The yarn is introduced into 1500 litres of water at C. The followingadditives are then introduced into the bath: 3000 g. of ammonium sulfate, 6000 g. of acetic acid (80% strength) and 9000 g. of the carrier preparation consisting of: 50 parts of the potassium salt of o-phenylphenol, 10 parts of levelling agent (1)(i), 10 parts of the reserve agent (2)- (a) and 30 parts of water. The pH-value is adjusted'to 4,5 with aceticacid.

o'nboth 'fibr'eportions results. l similargood results are obtained if carrier prepara- 8 The following dyestuffs are then added: 2000 g. of the dyestu fi of formula CHzCHn O F C (10) (h) N H:

O CH:

1450 g. of the dyestufi of formula Br Br 7 ofthe .dyestuff of formula I mo-noocNH Br Br SOzH The bath is then warmed to 103 c. within.45 minutes and dyeing' is carried out for 40 minutes at this temv rature. bath is" then cooled to C., the pH- v'al-ue increased to 8 with ammonia, and the goods treated in this bath for 20 minutes. They are then rinsed and dried. A fast reddyeing 'with good matching of the shade tions are used'which' contain the'levelling agents (1)-'(e),

"'(f )="'a'iid (i) and the reserve agents (2)-(e), (g) and I EXAMPLE 5 I v l0i0 kg of woven. fabric of 55% polyester and 45% woollare warmed to 60C. in 4000 litres of waterin a winch tank. The following additives are then. intro- 'dliced into the bath: 8000 g. of ammonium sulphate, 000'g.'.- of ..85% strength formic acid, and 5000 g. of

the. carrier preparation of the following composition:

i 40' p'arts of thesodium. salt of o-phenylphenol, 15 parts 'of l'evelling agent na 15 parts of reserve agent (2)- (a) and '30 parts of water. The pH-value of the bath is adjusted to 5 with formic acid. The following dyestuffs are then added: 1000 g. of the dyestufi of formula ornocm-cm-nn-h and 1500 g. of the dyestuff of formula HzN OH I I The bath is warmed to a high temperature within 45 minutes and dyeing is carried out for 60 minutes at this temperature. Thereafter the goods are rinsed and postwashed in a fresh bath at 80 C. as follows:

Bath additives: 2 g./l. of 85% strength formic acid and 2 g./l. of the leveling agent (1)-(b).

Time: 30 minutes.

Thereafter the goods are rinsed and dried. A fast dyeing with a two-color effect results, the polyester fibre being dyed blue whilst the wool is dyed red.

Equally good results are obtained if instead of the indicated carrier preparation the following carrier preparations are used:

(1) 30 parts of the sodium salt of o-phenylphenol, parts of levelling agent (1)-(b), parts of reserve agent (2)-(a) and 45 parts of water.

(2) 50 parts of the sodium salt of o-phenylhpenol, 10 parts of levelling agent (1)-(a), 10 parts of reserve agent (2)-(f) and 30 parts of water.

(3) 50 parts of the sodium salt of o-phenylphenol, 10 parts of levelling agent (1)-(f), 10 parts of reserve agent (2)-(h) and 30 parts of water.

(4) 50 parts of the sodium salt of o-phenylphenol, 10 parts of levelling agent (1)-(i), 10 parts of reserve agent (2)-(h) and 30 parts of water.

What is claimed is:

1. A process for simultaneously dyeing fibre mixtures of polyesters and wool, wherein the polyester portion is dyed with dispersion dyestuifs and the wool with wool dyestuffs in the presence of o-phenylphenol as a carrier, which comprises adding to the dyebath containing said dyestufis from 10 to about 40% of the weight of material being dyed of a carrier preparation comprising (a) to about 60% of the sodium or potassium salt of o-phenylphenol,

(b) 5 to about 20% of a levelling agent comprising the addition product of 5 to 70 mols of ethylene oxide to monoamines or diamines, with at least one nitrogen atom of the amine being substituted by an alkyl radical having 16 to 22 carbon atoms and wherein at least one nitrogen atom is quaternized and at least one polyglycol chain is esterified with a polybasic acid, and

(c) 2 to 20% of a wool reserve agent comprising the condensation product of formaldehyde, and

(a) sulphones which possess two hydroxy phenyl groups bonded to the S0 group, or

(b) hydroxybenzenesulphonic or naphthalene-sulphonic acids,

wherein the ratio (a):(b):(c) is in the range (20 to ii N H:

10 60) :(5 to 20):(2 to 20), and wherein the dyebath contains 2 to 15% of the sodium or potassium salt of ophenylphenol, relative to the weight of material being dyed.

2. Process according to claim 1 in which the dyeing is carried out at to C.

3. Process according to claim 1 in which the levelling agents consist of a mixture of an addition compound having at least one quaternized nitrogen atom and an addition compound having at least one polyglycol chain which is esterified by a polybasic acid.

4. Process according to claim 1 in which the carrier preparation is added to the dyebaths which contains, as the wool reserve agent having aflinity for the fibre, condensation products of formaldehyde and mixtures of (a) sulphones which possess two phenol residues bonded to the S0 group and (b) hydroxybenzenesulphonic or naphthalenesulphonic acids.

5. Process according to claim 4 in which the hydroxybenzenesulphonic acids of component (b) are phenolsulphonic and cresolsulphonic acids.

6. Process according to claim 1 in which a carrier preparation is added to the dyebaths which contain, as a wool reserve agent having afiinity for the fibre condensation products of formaldehyde and sulphones of formula @Ids wherein R and R independently of one another denote hydrogen atoms, methyl groups or sulphonic acid groups.

7. Process according to claim 4 characterized in that the molecular quantity ratio of (a) sulphone condensation product to (b) sulphonic acid condensation product in the reserve agent is 30:70 to 85:15.

8. A stable aqueous carrier preparation according to claim 1 which comprises (a) the sodium or potassium salt of o-phenylphenol, (b) at least one addition compound of 5 to 70 mols of ethylene oxide to monoamines or diamines, with at least one nitrogen atom of the amine being substituted by an alkyl radical of 16 to 22 carbon atoms, as a levelling agent and (c) at least one condensation product of formaldehyde and (a) sulphones which possess two hydroxy phenyl groups bonded to the SO;,- group and/or (b) hydroxylbenzene-sulphonic or naphthalenesulphonic acids, as a wool reserve agent having affinity for the fibre, with the quantity ratio (a):(b):(c) lying in the range (20 to 60):(5 to 20):(2 to 20) and with the dyebath containing 2 to 15 relative to the material to be dyed, of the sodium or potassium salt of o-phenylphenol.

References Cited UNITED STATES PATENTS 2,999,731 '9/ 1961 Harding 854 3,097,040 7/1963 Casty 8-54 3,097,047 7/ 1963 Weinstein et a1 8-94 3,528,761 9/1970 Keller et al 8-172 X OTHER REFERENCES Cheetham: Dyeing Fiber Blends, 1966, p. 283.

Diserens: Vol. I I, Chem. Tech. Dye. and Print., 1951, p. 78.

Bird: Theory and Practice of Wool Dyeing, 1963, pp. 177-179.

Trotman: Dye. and Chem. Tech. of Tex. Fibers, 1964, pp. 523-524.

HERBERT B. GUYNN, Primary Examiner B. H. HESS, Assistant Examiner US. Cl. X.R. I 8-25, 26, 89, 173 

